四个基于酰腙配体的双核苄基锡配合物的合成、晶体结构及体外抗癌活性

通过微波"一锅法"合成了4个双核苄基锡配合物:{[C_4H_3S(O)C=N-N=C(Me)COO](PhCH_2)_2Sn(MeOH)}_2(C1)、{[C_4H_3S(O)C=NN=C (Me)COO](p-Cl-C_6H_4CH_2)_2Sn (MeOH)}_2(C2)、{[C_4H_3S (O)C=N-N=C (PhCH_2)COO](PhCH_2)_2Sn (MeOH)}_2(C3)、{[C_4H_3S (O)C=N-N=C(PhCH_2)COO](p-Cl-C_6H_4CH_2)_2Sn(MeOH)}_2(C4),利用元素分析、IR、~1H NMR、~(13)C NMR、~(119)Sn NMR、HRMS以及X射线单晶衍射等表征了配合物结构。4个配合物分子均为双锡核分子,以Sn_2O_2四元环为中心对称,且中心锡原子与配位原子形成七配位畸变五角双锥构型。测试了配合物C1～C4的热稳定性以及配合物对癌细胞H460、HepG2、MCF7的体外抑制活性,结果表明:配合物C2是4个新合成的配合物中抑制癌细胞效果最好的化合物。     

二正丁基锡邻二茂铁基苯甲酸酯配合物的合成、表征及其体外抗癌活性

用2－Fe-C6H4CO2H和(n-Bu)2SnO反应合成了（2－Fe-C6H4CO2)2Sn(n-Su)2(A)和{[2-Fe-C6H4O2)Sn(n-Bu)2]2O}(B)(Fe=（η^5-C5H5)Fe(η^5-C5H4)两种新的二正丁基锡配合物,并用元素分析,红外光谱和核磁共振（1H,13C）谱等方法对配合物的组成和结构进行了表征,由此推测出配合物可能的分子结构,测定了配合物的体外抗癌活性,结果表明配合物对HL－60,HCT,BGC－823,KB等癌细胞均有很好的抑制能力。     

一种酰腙Schiff碱及其镉配合物的合成、晶体结构及体外抗癌活性的研究

2-硝基苯甲醛与异烟肼在无水乙醇中反应合成了1种异烟酰腙化合物C₁₃H₁₀N₄O₃并培养了单晶,采用X-射线单晶衍射法测定了其晶体结构,结果表明,它的一水合物C₁₃H₁₀N₄O₃·H₂O（1）的晶体属正交晶系,空间群Pna2₁,晶胞参数：a=1.5699（4）nm,b=0.71612（17）nm,c=1.1399（3）nm,V=1.2815（5）nm³,Z=4,Mr=288.27,D_c=1.494g·cm^-3,F（000）=600。采用常规溶液挥发法制备了该酰腙的镉配合物[Cd（H₂O）₄（C₁₃H₁₀N₄O₃）₂]（NO₃）₂（2）,化合物2的晶体属单斜晶系,空间群P2₁/n,晶胞参数：a=0.78248（13）nm,b=1.7398（3）nm,c=1.2080（2）nm,β=98.570（3）°,V=1.626.2（5）nm³,Z=2,Mr=848.99,D_c=1.734g·cm^-3,F（000）=860。同时,化合物经元素分析、红外光谱、紫外光谱和热重分析进行了表征。初步测试了二者的体外抗癌活性,结果表明2对人结肠癌细胞SW620有较强的增殖抑制作用。     

一种酰腙Schiff碱及其镉配合物的合成、晶体结构及体外抗癌活性的研究

2-硝基苯甲醛与异烟肼在无水乙醇中反应合成了1种异烟酰腙化合物C13H10N4O3并培养了单晶,采用X-射线单晶衍射法测定了其晶体结构,结果表明,它的一水合物C13H10N4O3·H2O(1)的晶体属正交晶系,空间群Pna21,晶胞参数:a=1.569 9(4)nm,b=0.716 12(17)nm,c=1.139 9(3)nm,V=1.281 5(5)nm3,Z=4,Mr=288.27,Dc=1.494 g·cm-3,F(000)=600。采用常规溶液挥发法制备了该酰腙的镉配合物[Cd(H2O)4(C13H10N4O3)2](NO3)2(2),化合物2的晶体属单斜晶系,空间群P21/n,晶胞参数:a=0.782 48(13)nm,b=1.739 8(3)nm,c=1.208 0(2)nm,β=98.570(3)°,V=1.626.2(5)nm3,Z=2,Mr=848.99,Dc=1.734 g·cm-3,F(000)=860。同时,化合物经元素分析、红外光谱、紫外光谱和热重分析进行了表征。初步测试了二者的体外抗癌活性,结果表明2对人结肠癌细胞SW620有较强的增殖抑制作用。     

哌嗪取代卟啉的合成、表征及其抗癌活性

设计并合成了6个具有抗癌活性的哌嗪取代卟啉化合物,分别为5,10,15,20-四[4-(4'-乙基哌嗪基)苯基]卟啉(TEPPH2,8a),5,10,15,20-四[4-(4'-丁基哌嗪基)苯基]卟啉(TBPPH2,8b),5,10,15,20-四[4-(4'-庚基哌嗪基)苯基]卟啉(THPPH2,8c),5,10,15,20-四[4-(4'-苯基哌嗪基)苯基]卟啉(TPhPPH2,8d),5-[4-(4'-乙基哌嗪基)苯基]-10,15,20-三苯基卟啉(EPTPPH2,8e)和5-[4-(4'-丁基哌嗪基)苯基]-10,15,20-三苯基卟啉(BPTPPH2,8f).这些卟啉化合物都由取代苯甲醛与吡咯缩合而成,每一个卟啉分子中含有一个或四个具有抗癌活性的取代哌嗪结构,结构经元素分析,MS,1H NMR,IR和UV-vis等表征.初步的生物活性研究表明,这些化合物具有一定的抗癌活性,因而在医学上可能具有潜在应用前景.     

两个三环己基锡芳香羧酸酯的合成、结构、热稳定性及体外抗癌活性研究

甲醇中三环己基氢氧化锡分别与呋喃-2-甲酸、2,4,6-三甲基苯甲酸反应,合成了2个三环己基锡芳香羧酸酯Cy3SnO2CC4H3O(1)和Cy3SnO2CC6H2Me3(2)(Cy为环己基)。通过IR、1H和13C NMR、元素分析及X-射线单晶衍射表征结构。1和2均属单斜晶系,配合物1空间群P21,晶体学参数:a=0.823 04(2)nm,b=1.111 19(3)nm,c=1.283 90(3)nm,β=101.090(2)°,Z=2,V=1.152 27(5)nm3,Dc=1.381 g·cm-3,μ(Mo Kα)=1.127 mm-1,F(000)=496,R1=0.052 9,wR2=0.138 7。配合物2空间群P21/c,晶体学参数:a=0.999 62(2)nm,b=1.415 97(2)nm,c=1.973 59(3)nm,β=94.042 0(10)°,Z=4,V=2.786 53(8)nm3,Dc=1.266 g·cm-3,μ(Mo Kα)=0.937 mm-1,F(000)=1 112,R1=0.0540,wR2=0.161 9。配合物(1)和(2)的中心锡原子均为畸变四面体构型。通过分子间氢键作用,配合物(1)形成二维网状结构。试验表明,配合物1和2具有良好的热稳定性,对人癌细胞Colo205、HepG2、MCF-7、Hela、NCI-H460增殖均有较强的抑制作用。     

两个三环己基锡芳香羧酸酯的合成、结构、热稳定性及体外抗癌活性研究

甲醇中三环己基氢氧化锡分别与呋喃-2-甲酸、2,4,6-三甲基苯甲酸反应,合成了2个三环己基锡芳香羧酸酯Cy₃SnO₂CC₄H₃O（1）和Cy₃SnO₂CC₆H₂Me₃（2）（Cy为环己基）。通过IR、¹H和¹³C NMR、元素分析及X-射线单晶衍射表征结构。（1）和（2）均属单斜晶系,配合物（1）空间群P2₁,晶体学参数：a=0.82304（2）nm,b=1.11119（3）nm,c=1.28390（3）nm,β=101.090（2）°,Z=2,V=1.15227（5）nm³,D_c=1.381g·cm^-3,μ（Mo Kα）=1.127mm^-1,F（000）=496,R₁=0.0529,wR₂=0.1387。配合物（2）空间群P2₁/c,晶体学参数：a=0.99962（2）nm,b=1.41597（2）nm,c=1.97359（3）nm,β=94.0420（10）°,Z=4,V=2.78653（8）nm³,D_c=1.266g·cm^-3,μ（Mo Kα）=0.937mm^-1,F（000）=1112,R₁=0.0540,wR₂=0.1619。配合物（1）和（2）的中心锡原子均为畸变四面体构型。通过分子间氢键作用,配合物（1）形成二维网状结构。试验表明,配合物（1）和（2）具有良好的热稳定性,对人癌细胞Colo205、HepG2、MCF-7、Hela、NCI-H460增殖均有较强的抑制作用。     

有机锡联苯乙酸酯的合成、结构表征和体外抗癌活性

合成了4个新的有机锡联苯乙酸酯{[(n-C₄H₉)₄Sn(O₂CCH₂C₆H₄C₆H₅-4)]₂O}₂ (1)和R₃SnO₂CCH₂C₆H₄C₆H₅-4(R=C₄H₅，2；c-C₆H₁₁，3；C₆H₅C(CH₃)₂CH₂，4)，利用元素分析、IR、 ¹H和 ¹³C NMR表征了其结构。通过X-射线单晶衍射测定了1和4的晶体结构。化合物1和化合物4均属三斜晶系，空间群P1。化合物1为具有Sn₂O₂四元环的中心对称二聚体结构，4为畸变的四面体结构。生物活性测试结果表明，化合物1和4对3种人癌细胞HeLa、CoLo205和MCF-7具有较好的体外抑制活性。     

甘草素的合成及其抗癌活性

以间苯二酚和对羟基苯甲醛为起始原料,经付克酰基化、羟基保护、羟醛缩合、Michael加成及脱保护反应合成了甘草素(1),总收率36.4%,其结构经1HNMR,13C NMR,IR和MS表征。采用MTT法,以5-氟尿嘧啶为阳性对照药,研究了1对人肺腺癌细胞,前列腺癌细胞(DU-145),人胃癌细胞,人结肠癌细胞(HCT-116)及肝癌细胞的抗癌活性。结果表明:1具有较好的抗HCT-116活性,对DU-145也表现了一定的抑制作用。     

4-(1,3,4-噻二唑-2-巯基)苯并[4,5]呋喃[3,2-d]嘧啶类衍生物合成、晶体结构及抗癌活性

从水杨腈出发,经醚化、两次成环、氯化制得4-氯-苯并[4,5]呋喃[3,2-d]嘧啶(5);5与5-取代-2-巯基-1,3,4-噻二唑反应,合成了7个新的含噻二唑的苯并[4,5]呋喃[3,2-d]嘧啶衍生物.其结构经1HNMR,13CNMR,IR和MS表征,培养并测定化合物6a的晶体结构.采用MTT法进行化合物抑制PC3癌细胞体外活性测试,结果表明所合成的化合物具有不同程度的抑制PC3癌细胞活性,其中化合物6b在10μmol?L-1浓度下对PC3的抑制率为89.2%.     

Di‐n‐butyltin aminoarylcarboxylates: structure,properties and in vitro antitumor activity

The properties and structures of the tetranuclear dibutyltin complexes [Sn₄(µ₃‐O)₂(C₄H₉‐n)₈­{OOCC₆H₃(NH₂)₂‐3,4}₄] (1), [Sn₄(µ₃‐O)₂(C₄H₉‐n)₈{OOCC₆H₃(NH₂)₂‐3,5}₄] (2), [Sn₄(µ₃‐O)₂(C₄H₉‐n)₈­{OOC‐2‐C₆H₄N?NC₆H₄N(CH₃)₂‐4}₄] (3) are described. Complex 3 adopts a structure with a tetranuclear Sn₄(µ₃‐O)₂ core. All tin atoms are five‐coordinate and form bonds with three oxygen atoms and two butyl ligands. Two carboxylates are bridging and two are terminal ligands. IR and NMR spectra indicate that the same structure is adopted by complexes 1 and 2. The molecular and electronic structures of complex 1 of C _i symmetry have been studied using the semi‐empirical PM3 formalism. The calculated structure and bond distances agree with X‐ray data. All complexes are effective antitumor agents. Copyright © 2002 John Wiley & Sons, Ltd.     

Synthesis,antitumor activity and crystal structure of the triphenyltin derivative of exo‐7‐oxa‐bicyclo[2,2,1]hept‐5‐ene‐3‐N‐p‐tolylamide‐2‐acid

The synthesis and crystal structure of­Ph₃SnO₂CCHCHCH:CHCH(O)CHCONHC₆H₄­CH₃·CH₂Cl₂ are reported. The monomer units­are bridged by the carbonyl oxygen of the amide group, thus forming a polymer in which each tin atom is best described as having a distorted five‐coordinate geometry. There is a relatively strong intramolecular hydrogen bond between the amide hydrogen and the ether oxygen. The in vitro antitumor activities of the title compound against HL‐60, BGC‐823, Bel‐7402, SKOV3, KB and Hela tumor lines are reported. The title compound shows a distinct advantage when the metal (tin) is introduced into the acid.Copyright © 2001 John Wiley & Sons, Ltd.     

有机锡4-(4-吡啶基甲基硫代)苯甲酸酯的合成、结构与生物活性研究

通过4-（4-吡啶基甲基硫代）苯甲酸与三苯基氧化锡以及三环己基氢氧化锡反应,合成了三苯基锡4-（4-吡啶基甲基硫代）苯甲酸酯（1）及三环己基锡4-（4-吡啶基甲基硫代）苯甲酸酯（2）。它们的结构通过红外,核磁以及X-射线单晶衍射分析得到确证。化合物1表现为一维链状结构,而化合物2通过分子间的O-H…O和O-H…N氢键形成二维网状结构。生物活性测试表明,这2个化合物具有较高的抗肿瘤活性。     

有机锡4-(4-吡啶基甲基硫代)苯甲酸酯的合成、结构与生物活性研究(英文)

通过4-(4-吡啶基甲基硫代)苯甲酸与三苯基氧化锡以及三环己基氢氧化锡反应,合成了三苯基锡4-(4-吡啶基甲基硫代)苯甲酸酯(1)及三环己基锡4-(4-吡啶基甲基硫代)苯甲酸酯(2)。它们的结构通过红外,核磁以及X-射线单晶衍射分析得到确证。化合物1表现为一维链状结构,而化合物2通过分子间的O-H…O和O-H…N氢键形成二维网状结构。生物活性测试表明,这2个化合物具有较高的抗肿瘤活性。     

双(三有机锡)2，3-吡啶二甲酸酯的合成、表征和体外抗癌活性

合成了2个新的双(三有机锡)2，3-吡啶二甲酸酯2，3-C₅H₃N(CO₂SnR₃)₂ (R=c-C₆H₁₁，1；C₆H₅C(CH₃)₂CH₂，2)，利用元素分析、IR和¹H NMR表征了其结构。通过X-射线单晶衍射测定了配合物2的晶体结构。该化合物晶体属单斜晶系，空间群P2₁/n，a=0.955 3(1)，b=1.811 8(2)，c=3.533 9(4) nm，β=94.914(2)°，Z=4，V=6.094 1(13) nm³，R=0.038 4，wR=0.096 6，S=1.015。2，3-吡啶二甲酸的2个羧基键连2个三有机锡，2个锡原子均为畸变的四面体配位构型。生物活性测试结果表明，化合物1和2对3种人癌细胞HeLa、CoLo205和MCF-7具有好的体外抗癌活性。     

Crystal Structure and Antitumor Activity of Tri[2- [N-(4''''-methyl-benzylsulfonyl)amino]ethyl]-amine

1 INTRODUCTION The supramolecular architectures of tripodal ligands with special cavities have attracted much attention of chemists and biochemists because of their interesting structures and possible properties such as ion and molecular recognition, selective inclusion and important biological function[1～5]. However, their potential applications in supra- molecular and biological chemistry for constructing various complexes have not been clearly realized until recent years. Few crystal…     

Synthesis, Characterization and Properties of Organotin Complexes Dibutyltin（Ⅳ） Bis（heteroaromatic carboxylate） and Crystal Structure of Dibutyltin（Ⅳ） Bis（2-thiazolylcarboxylate）

The six organotin complexes dibutyltin(IV) bis(heteroaromatic carboxylate) were synthesized by the reaction of (n‐Bu)2SnO with heteroaromatic carboxylic acid in 1:2 molar ratio. These complexes have been characterized by elemental analysis, IR, ¹H, ¹³C and ¹¹⁹Sn NMR. The crystal structure of dibutyltin(IV) bis(2‐thiazolylcarboxylate) was determined by X‐ray single crystal diffraction. This compound is a weakly bridged dimer through weak interaction Sn···O between molecules. The tin atoms took six‐coordinate skew‐trapezoidal bipyramidal geometry. The crystal of complex 3 belongs to monoclinic symmetry with space group P2₁/c, a=1.863(2) nm, b=2.220(3) nm, c=1.0395(10) nm, β=90.275(16)°, Z=8, V=4.292(8) nm³, D_c=1.514 Mg/m³, μ=1.406 mm^‐1, F(000)=1968, S=0.999, R=0.0549, wR=0.1011.     

Crystal Structure and Antitumor Activity of Tri[2-[N-（4′-methyl-benzylsulfonyl）amino]ethyl]-amine

The crystal structure of the title compound (C27H38N4O7S3, Mr = 626.79) has been determined by single-crystal X-ray diffraction. The crystal is of triclinic, space group Pīwith a = 9.411(1), b = 11.645(2), c = 14.672(2) (A。), α = 91.80(1), β = 95.36(1), γ =104.56(1)o, V = 1547.0 (A。)3, Z = 2, Dc = 1.346 g/cm3, λ = 0.71073 (A。), μ(MoKα) = 0.289 mm－1 and F(000) = 664. The structure was refined to R = 0.0406 and wR = 0.1177 for 4103 observed reflections with I > 2σ(I). X-ray diffraction analysis reveals that the title compound is a practically distorted tetrahedron and each molecule contains one lattice H2O by hydrogen bond. The antitumor activity of the title compound against HL-60 human leukemia cells has also been studied by MTT method.     

Synthesis and Crystal Structure of Bis[（2,6—pyridinedicar—boxylato）（methanol）dibenzyltion（Ⅳ）]

A novel seven‐coordinate dimer bis[(2,6‐pyridinedicarboxylato)(methanol)dibenzyltin(IV)] was synthesized by the reaction of (PhCH₂)₃SnCl with 2,6‐pyridine dicarboxylic acid in 1:1 molar ratio in methanol solution. The structure was characterized by elemental analysis, IR and ¹H NMR spectra, and the crystal structure was determined by X‐ray single crystal diffraction analysis. The crystal belongs to monoclinic space group P2₁/n, a =0.96250(19) nm, b = 1.0947(2) nm, c = 1.9965(4) nm, β = 92.31(3)°, Z = 2, V = 2.1019(7) nm³, D_c = 1.574 g/cm³, μ = 1.248 mm^?1, F(000)=1000, R₁ = 0.0675, wR₂ = 0.0836. In the crystals of the complex, each tin atom is seven‐coordinated in a distorted bipyramidal structure.     

Synthesis and Crystal Structure of Di-n-butyltin（Ⅳ） Complex with 2-Oxo-propionic Acid （4-Pyridinecarbonyl） Hydrazone

The novel complex di‐n‐butyltin(IV) 2‐oxo‐propionic acid (4‐pyridinecarbonyl) hydrazone, (n‐C₄H₉)₂Sn‐[O₂CC(CH₃)=N‐N=C(‐O)C₅N‐4] (H₂O) has been synthesized and its structure has been determined by X‐ray diffraction analysis. The complex crystallizes in orthorhombic system with space group Pca2₁. Crystal data: a=2.7540(9) nm, b=0.9676(3) nm, c= 1.5750(5) nm, V=4.197(2) nm³, D_c= 1.444 g/cm³, Z=8. μ= 1.241 mm^?1. F(000)= 1856, R₁=0.0462 and wR₂=0.1001. In the crystals of the title complex, the tin atom is in six‐coordination with a distorted octahedral geometry, three oxygen atoms [O(1), O(3) and O(4)] and one nitrogen atom N(1) forming the equatorial plane and C(10)‐Sn(1)‐C(14) being the axis. Two molecules form a dimer with weak interactions of Sn‐O bonding and hydrogen bonds.